Polymer-zeolite nanocomposite membranes for proton-exchange-membrane fuel cells

ABSTRACT

A suite of polymer/zeolite nanocomposite membranes. The polymer backbone is preferably a film forming fluorinated sulfonic acid containing copolymer, such as a Teflon type polymer, a perfluorinated polymer, or a perfluorinated polymer with sulfonic groups. The zeolites formed in accordance with the present invention and which are used in the membranes are plain, phenethyl functionalized and acid functionalized zeolite FAU(Y) and BEA nanocrystals. The zeolite nanocrystals are incorporated into polymer matrices for membrane separation applications like gas separations, and in polymer-exchange-membrane fuel cells. For the purpose of developing zeolite-polymer nanocomposite membranes, the zeolite nanocrystals are size-adjustable to match the polymer-network dimensions.

CROSS-REFERENCES TO RELATED APPLICATIONS

The present application is a division of U.S. patent application Ser.No. 10/982,708, filed Nov. 5, 2004 now U.S. Pat. No. 7,691,514, whichclaims priority to U.S. Provisional Patent Application No. 60/518,406,filed Nov. 7, 2003, the teachings of which are incorporated herein byreference for all purposes.

BACKGROUND OF THE INVENTION

The present invention relates to the formation of polymer/zeolitenanocomposite membranes, and in particular to using such membranes forfuel cell applications.

Proton exchange membrane fuel cell (PEMFC) systems have been determinedto be approximately two to three times as efficient as conventionalinternal combustion engine (ICE) power systems. The power density,volume and weight of PEMFC systems approach that of an ICE power system,making PEMFC systems ideal for transportation applications. PrototypePEMFC vehicles have shown that hydrogen fed, PEMFC powered vehicles arecapable of performance comparable with ICE vehicles in all respects,however the cost of a mass produced PEMFC system is currently 10 timesgreater than a comparable ICE power system, and no national hydrogenrefueling network exists. Fuel cell cost is expected to come down as thetechnology is developed further, but the costs associated withdeveloping a hydrogen distribution network would be tremendous.

However, there would be no need for a new national distribution network,if either reformed hydrogen or methanol fed PEMFC powered vehicles wereused, because a liquid hydrocarbon (gasoline) distribution network isalready in place. PEMFCs can be run on hydrogen gas generated byreforming a liquid hydrocarbon fuel such as methanol, ethanol orgasoline, as long as carbon monoxide levels in the hydrogen feed streamare reduced to less than 10 ppm. Use of feed hydrogen with more than 10ppm CO causes anode catalyst poisoning and fuel cell performancesuffers. Unfortunately, system bulk and complexity required to reduce COlevels in the hydrogen feed gas to 10 ppm during steady operation and100 ppm during transient operation makes it impractical for use in avehicle. Interestingly, use of both reformed hydrogen fed PEMFC powerplants could be realized if the temperature operation range of theirproton exchange membrane material was extended from 80° C. up to 140° C.CO tolerance of the PEMFC anode catalyst has been shown to increasegreatly with temperature, and would eliminate the need for bulky COremoval equipment for the reformed hydrogen feed stream. In addition,higher temperature operation can also facilitate thermal management/heatutilization of the fuel cell stack, and potentially simplify fuel cellwater management. However, current proton exchange membranes are notsuitable for operation at these temperatures due to dehydration problemsand mechanical instability. One of the major technology breakthroughsrequired for PEMFCs is a membrane material that operates at highertemperatures.

Direct methanol fuel cells (DMFCs), which take liquid methanol insteadof H₂ fuel, enjoy a competitive advantage over H₂-air fuel cell systemin terms of the refueling infrastructure, storage/transport system andsafety concerns. DMFC is especially promising for powering portableelectronics such as cell phones and laptop computers. The crossover ofmethanol through the polymer electrolyte membrane and the low activityof the reported Pt based catalyst for methanol oxidation limitperformance of DMFCs and restrict their potential applications. In teensof methanol crossover, besides the loss of fuel, another disadvantage isthat it will lead to a significant performance loss due to the formationof “mixed potentials”, as a result of concurring of oxygen reduction andmethanol oxidation on the Pt cathode electrocatalysts.

Experimental results show that methanol crossover through Nafionmembrane leads to a significant performance loss in DMFC and thisphenomenon is more severe with the increase of methanol feedconcentration. Therefore, there exists a need to develop a compositemembrane that is able to reduce the methanol crossover while stillmaintaining its high proton conductivity; a membrane that is able tocombine the high proton conductivity of a polymer with the hydration andmechanical stability of an inorganic material in order to get a membranecapable of elevated (e.g., 140° C.) operation.

One promising strategy for efficient proton conduction and methanolblocking at elevated temperatures is to incorporate inorganicnanoparticles inside the membrane. Previous attempts were based on theidea of combining the high proton conductivity of Nafion with thethermally stable, hydrophilic material, such as silica, in order tomaintain hydration at high temperatures and to physically block methanolcrossover. However, introducing silica dilutes the sulfonic acid numberconcentration, resulting in a loss in membrane proton conductivity. Anideal composite membrane additive would be able to increase the protonconcentration, while still improving hydration/mechanical properties andblocking methanol crossover at high temperatures.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed towards a suite of polymer/zeolitenanocomposite membranes. The polymer backbone is preferably a filmforming fluorinated sulfonic acid containing copolymer, such as a Teflontype polymer, perfluorinated polymer, or perfluorinated polymer withsulfonic groups. The zeolites formed in accordance with the embodimentsof the present invention and which are used in the membrane are plain,phenethyl functionalized and acid functionalized zeolite FAU(Y) and BEAnanocrystals. The zeolite nanocrystals are incorporated into polymermatrices for membrane separation applications like gas separations, andin polymer-exchange-membrane fuel cells. For the purpose of developingzeolite-polymer nanocomposite membranes, the zeolite nanocrystals aresize-adjustable to match polymer-network dimensions.

The polymer-zeolite nanocomposite membranes in accordance with theembodiments of the present invention take advantage of the molecularsieving and proton conductivity of sulfonic acid functionalized zeolitenanocrystals. Results indicate that the methanol crossover of the 5 wt %nanocomposite membranes is 45% lower and proton conductivity is 17%higher than a commercial Nafion 117 membrane at 80° C. and 100% relativehumidity. The nanocomposite membranes in accordance with the embodimentsof the present invention have the potential to maintain high protonconductivity and low methanol crossover at temperatures up to 140° C.;improving anode kinetics, reducing anode CO poisoning, improvingmethanol oxidation efficiency, and reducing cathode overpotentials inPEMFCs.

For a further understanding of the nature and advantages of theinvention, reference should be made to the following description takenin conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the polarization curves for direct methanol fuel cells (DMFCs)with different membranes. Operating condition: 70° C., oxygen pressure26 psi. anode: 1 mg/cm² 40% PtRu/C; cathode: 0.5 mg/cm², 20% Pt/C.

FIG. 2 is a transmission electron microscopy image of the sizecontrolled zeolite FAU(Y) nanocrystals.

FIG. 3 shows a Si²⁹ NMR analysis of the plain and phenethylfunctionalized zeolite FAU(Y) nanocrystals. The additional peak locatedat −65 ppm indicates the presence of zeolite framework Si atoms that arecovalently bonded to a phenethyl side chain.

FIG. 4 shows a Si²⁹ NMR analysis of the phenethyl functionalized zeoliteBEA nanocrystals. The peak located at −65 ppm indicates the presence ofzeolite framework Si atoms that are covalently bonded to a phenethylside chain.

FIG. 5 shows a transmission electron microscopy image of the phenethylfunctionalized zeolite BEA nanocrystals synthesized with the followingcomposition 1.00 Al₂O₃:(v*(1−w)) SiO₂(HS−30):(v*w)SiO₂(PETMS):(0.26*v+1) (TEA)₂O (2OH⁻):(15*v) H₂O, where v=25, andw=0.028.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions

Unless defined otherwise, all technical and scientific terms used hereinhave the meaning commonly understood by a person skilled in the art towhich this invention belongs. As used herein, the following terms havethe meanings ascribed to them unless specified.

Zeolites are catalytic and separation materials that can havenanostructures on the same scale as the molecules that react and adsorbwithin their pores. Their nanostructure is a function of the conditionsunder which they are created, and because of the molecular scale of thecatalytic and separation surfaces, their macroscopic properties are thusa function of those same conditions.

Zeolites are microporous crystalline oxides with a high surface tovolume ratio. They are aluminosilicates of formM_(x)*(Si_(1−x)+Al_(x))O₂*yH₂O, (Here M is monovalent metal ion) but mayalso include many zeolite-like materials that are also microporous, suchas aluminophosphates, zincosilicates, and titanosilicates. Zeolites areactually natural products. Not all naturally occurring zeolites havebeen recreated in the laboratory, and conversely, many zeolites havebeen synthesized that do not occur in nature. Zeolite synthesis is notsimilar to synthetic organic chemistry. The zeolite is assembled througha series of non-equilibrium molecular recognition events that cannot beunderstood in the same dot-and-arrow schema that synthetic organicschemes are constructed from. In fact, this process is still not wellunderstood.

OFMS—Organic Functionalized Molecular Sieves. In order to try to broadenthe types of reactions that microporous and mesoporous materials cancatalyze, researchers would like to be able to chemically functionalizetheir materials. Although this notion has been successful to someextent, for instance in the case of grafting organosilanes that containorganic functional groups onto the internal surfaces of mesoporousmaterials, there has been little success repeating the process formicroporous materials.

Electrolytes: The “electrolyte” is that part of any fuel cell thatseparates the anode and the cathode. Positively and negatively chargedspecies (e.g., protons and electrons in a PEMFC) are formed by catalysisof the fuel (hydrogen) at the anode, and the electrolyte allows theprotons but not the electrons to pass through to the cathode, andforcing the electrons to reach the cathode through an external circuitwhere the electrons can do work as electricity. The electrolyte used iswhat gives a particular type of fuel cell its name: alkaline, moltencarbonate, phosphoric acids, PEM, solid oxide, etc.

Proton Exchange Membrane Fuel Cell (PEMFC): Proton exchange membrane(PEM) fuel cells work with a polymer electrolyte in the form of a thinsheet. This membrane is small and light, and it works at lowtemperatures (about 80 degrees C., or about 175 degrees F.). Otherelectrolytes such as solid oxide fuel cell electrolyte can requiretemperatures as high as 1,000 degrees C. Catalysts are used at both theanode and cathode on either side of the membrane to carry out thenecessary reactions for the fuel cell to generate electricity. Hydrogenmolecules are stripped of their electrons at the anode, and thepositively charged protons diffuse through polymer membrane and migratetoward the cathode. The electrons pass from the anode to the cathodethrough an exterior circuit and perform electrical work along the way.At the cathode, the electrons, protons and oxygen from the air combineto form water. For the fuel cell to work, the proton exchange membraneelectrolyte must allow protons to pass through but prohibit theconduction of electrons and permeation of gases.

II. Methods of Forming Polymer/Zeolite Nanocomposite Membranes

Embodiments of the present invention are directed towards a suite ofpolymer/zeolite nanocomposite membranes. The polymer backbone ispreferably a film forming fluorinated sulfonic acid containingcopolymer, such as a Teflon type polymer, perfluorinated polymer, andperfluorinated polymer with sulfonic groups. The zeolites used in themembrane are plain, phenethyl functionalized and acid functionalizedzeolite FAU(Y) and BEA nanocrystals. The zeolite nanocrystals areincorporated into polymer matrices for membrane separation applicationslike gas separations, and in polymer-exchange-membrane fuel cells. Forthe purpose of developing zeolite-polymer nanocomposite membranes, it isalso desirable that zeolite nanocrystals are size-adjustable to matchpolymer-network dimensions.

The following examples are provided to illustrate the embodiments of thepresent invention. They are not intended to limit the scope of thisdisclosure to the embodiments exemplified therein. All ranges for allparameters disclosed are inclusive of the range limits.

EXAMPLE Preparation of Colloidal Zeolite FAU(Y) Nanocrystals

The preparation scheme for hydrothermal synthesis of colloidalsuspensions of zeolite FAU(Y) nanocrystals is described below. First a250 mL polypropylene bottle containing a magnetic stir bar was washedwith double deionized water (DDI H₂O) using ultrasonication. Thenappropriate amounts of double deionized water (DDI H₂O), 25 wt % aqueoustetramethylammonium hydroxide solution (TMAOH), and aluminumisopropoxide (97 wt %) were added, in that order, and stirred vigorouslyuntil the solution became clear. Tetramethylammonium bromide (TMABr, 98wt %) was then added to the clear solution and stirred until completelydissolved. Aqueous 30 wt % colloidal silica (Ludox HS-30, SiO₂/Na₂O=90,wt % SiO₂=29.90, wt % Na₂O=0.34) was then added to complete thesolution, and the bottle was sealed tightly. The molar composition ofthe synthesis solution in general was 1.00 Al₂O₃:4-5 SiO₂:2-3 (TMA)₂O(2OH⁻):0-3 (TMA)₂O(2Br⁻):0.044-0.055 Na₂O:200-300 H₂O. After each batchwas sealed, it was aged for 3 days at room temperature (RT) withvigorous stirring, and was then heated with stirring in a 100° C. oilbath. Periodic 10 mL samples were taken during the synthesis by quicklyopening, sampling, and resealing the bottle. All samples were washed bythree repetitions of centrifugation with relative centrifugal force of48,500 g for 2 hours; then decanting, and redispersion in DDI H₂O withultrasonication before analyses preparations were performed.Centrifugation were performed in a Beckman J2-HS centrifuge at 20,500rpm using a JA-21 rotor.

Using the above procedure, zeolite nanocrystals are synthesized usingtetramethyl ammonium bromide (TMABr) as an additional organic template.An example solution composition is 1.00 Al₂O₃-4.35 SiO₂-2.40(TMA)₂O(2OH⁻)-1.2 (TMA)₂O(2Br⁻)-0.048 Na₂O-249.00 H₂O, with a weightcomposition of 76.5 g DDI H₂O, 52.3 g TMAOH, 11.3 g TMABr, 12.5 galuminum isopropoxide, and 26.2 g Ludox HS-30.

Using this method, average nanocrystal size is controllable in the rangeof 32-45 nm by manipulating tetramethylammonium concentration and anionconcentration. A transmission electron microscopy image of the sizecontrolled zeolite FAU(Y) nanocrystals is provided in FIG. 2 The averageparticle size of the crystals in the TEM image is 32 nm, which agreedvery well with the 33 nm average particle size obtained during dynamiclight scattering particle analyses on the same sample. By using thismethod, a high nanocrystal yield was obtained. For example, crystalshydrothermally synthesized with a 1.00 Al₂O₃-4.35 SiO₂-2.40(TMA)₂O(2OH—)-1.2(TMA)₂O(2Br—)-0.048 Na₂O-249.00 H₂O (T3.6) solutioncomposition were 45% smaller by volume after 54 hours of crystallizationat 100° C. and were obtained with approximately 73% more yield (gzeolitic Al₂O₃+SiO₂/g synthesis Al₂O₃+SiO₂) than crystals synthesizedwith a 1.00 Al₂O₃-4.35 SiO₂-2.40 (TMA)₂O(2OH—)-0.048 Na₂O-249.00 H₂O(T2.4) composition. After 216 hours, T3.6 syntheses contained 37 nmcrystals with 180% higher yield than that of T2.4 syntheses at 54 hours(38 nm crystals, 0.044 g zeolitic Al₂O₃+SiO₂/g synthesis Al₂O₃+SiO₂).

EXAMPLE Preparation of Phenethyl Functionalized Colloidal Zeolite FAU(Y)Nanocrystals

The preparation scheme for hydrothermal synthesis of phenethylfunctionalized colloidal suspensions of zeolite FAU(Y) nanocrystals wasas follows: First a 250 mL polypropylene bottle containing a magneticstir bar was washed with double deionized water (DDI H₂O) underultrasonication. Then appropriate amounts of DDI H₂O, 25 wt % aqueoustetramethylammonium hydroxide solution (TMAOH, SACHEM), and aluminumisopropoxide (97 wt %, Aldrich) were added, in that order, and stirredvigorously until the solution became clear. Tetramethylammonium bromide(TMABr, 98 wt %, Fisher) was then added to the clear solution andstirred until completely dissolved. Aqueous 30 wt % colloidal silica(Ludox HS-30, SiO₂/Na₂O=90, wt % SiO₂=29.90, wt % Na₂O=0.34, Aldrich)was then added. Then an appropriate amount of phenethyl trimethoxysilane(PETMS, 98 wt %, Aldrich) was added to complete the solution, and thebottle was sealed tightly. The molar composition of the synthesissolution in general was 1.00 Al₂O₃:3-5 SiO₂(HS-30):0.12-1.45SiO₂(PETMS):2-3 (TMA)₂O (2OH⁻):0-3 (TMA)₂O(2Br⁻):0.044-0.055Na₂O:200-300 H₂O. After each batch was sealed, it was aged for 3 days atroom temperature (RT) with vigorous stirring, and was then heated withstirring in a 100° C. oil bath. Periodic 10 mL samples were taken duringthe synthesis by quickly opening, sampling, and resealing the bottle.

Using the above procedure, phenethyl functionalized zeolite FAU(Y)nanocrystals are synthesized using tetramethyl ammonium bromide (TMABr)as an additional organic template and PETMS as a functionalized silicasource. The composition of an example solution is 1.00 Al₂O₃-4.35SiO₂-0.12 SiO₂(PETMS)-2.40 (TMA)₂O(2OH⁻)-1.2 (TMA)₂O(2Br⁻)-0.048Na₂O-249.00 H₂O, with a weight composition of 76.5 g DDI H2O, 52.3 gTMAOH, 11.3 g TMABr, 12.5 g aluminum isopropoxide, 26.2 g Ludox HS-30,and 0.84 g phenethyltrimethoxysilane (PETMS).

Using this method, phenethyl functionalized zeolite FAU(Y) nanocrystalswere formed. Phenethyl functionization was verified using Si magic anglespinning nuclear magnetic resonance spectroscopy (Si²⁹ NMR). FIG. 3shows a Si²⁹ NMR analysis of the plain and phenethyl functionalizedzeolite FAU(Y) nanocrystals. The additional peak located at −65 ppmindicates the presence of zeolite framework Si atoms that are covalentlybonded to a phenethyl side chain. This verifies a proper formation forthe phenethyl functionalized zeolite FAU(Y) nanocrystals.

EXAMPLE Preparation of Phenethyl Functionalized Colloidal Zeolite BEANanocrystals

Synthesis of phenethyl functionalized zeolite BEA nanocrystals wasconducted using two separate techniques. In the first technique, a 250mL polypropylene bottle containing a magnetic stir bar was washed withdouble deionized water (DDI H₂O) under ultrasonication. Then appropriateamounts of DDI H₂O, 35 wt % aqueous tetraethylammonium hydroxidesolution (TEAOH), and aluminum isopropoxide (97 wt %) were added, inthat order, and stirred vigorously until the solution became clear.Aqueous 30 wt % colloidal silica (Ludox HS-30, SiO₂/Na₂O=90, wt %SiO₂=29.90, wt % Na₂O=0.34) was then added. The appropriate amount ofphenethyl trimethoxysilane (PETMS, 98 wt %, Aldrich) was added tocomplete the solution, and the bottle was sealed tightly. The finalmolar composition of any given synthesis solution was 1.00Al₂O₃:100*(1-x) SiO₂(HS-30):100*(x) SiO₂(PETMS):18 (TEA)₂O (2OH⁻):1.11Na₂O:1330 H₂O. The mole percentage of the total Si in the synthesismixture provided by PETMS is represented by x. A typical batch weightcomposition is as follows: (for x=0.005) 76.46 g TEAOH, 12.5 g aluminumisopropoxide, 100.5 g Ludox HS-30, and 0.58 g phenethyl trimethoxysilane(PETMS). After each batch was sealed, it was aged for 2 hours at roomtemperature (RT) with vigorous stirring, and was then heated withstirring in a 100° C. oil bath. Periodic 10 mL samples were taken foranalysis during the synthesis by quickly opening, sampling, andresealing the bottle.

The second technique to synthesize phenethyl functionalized zeolite BEAnanocrystals began with a ten-minute hydrofluoric acid soak of the 35 mLTeflon liner in a stainless steel cased Parr autoclave. The Teflon linerwas then rinsed and scrubbed thoroughly with Alconox and DDI H₂O. Priorto the addition of the reaction mixture to the autoclaves, the mixtureswere prepared in polypropylene bottles, with stirring by magnetic bars.Two precursor solutions, one with aluminum and the other containingsilica, were prepared for each reaction batch. The aluminum precursorsolution was composed of Al powder (99.95% Al) and half of the requiredTEAOH (35 wt %). The silica precursor solution was composed of theremaining half of the recipe's TEAOH, DDI H₂O, fumed silica, andphenethyl trimethoxysilane (PETMS, 99.8%). Both solutions were stirredvigorously until the aluminum solution became clear, indicating thecomplete hydrolyzation of the aluminum powder. The solutions were mixedtogether in one bottle for 1 hour at room temperature, and then pouredinto a Teflon liner, and sealed inside a stainless steel autoclave. Thefinal molar composition of any given synthesis solution was 1.00Al₂O₃:(v*(1-w)) SiO₂(fumed silica):(v*w) SiO₂(PETMS):(0.26*v+1) (TEA)₂O(2OH⁻):(15*v) H₂O. The total SiO₂/Al₂O₃ ratio is represented by thesymbol v. The mole percentage of total Si in the synthesis mixtureprovided by PETMS is represented by w. A typical batch weightcomposition is as follows: (for v=25, w=2.8%), 20.15 g TEAOH, 0.1646 galuminum powder, 4.96 g fumed SiO₂, and 0.54 g PETMS. The autoclave wasthen inserted into a custom tumbling apparatus spinning end over end at70 revolutions per minute within a convection oven at 140° C. Reactiontimes as long as 14 days were required for batches with v=25.

All samples were washed by three repetitions of centrifugation withrelative centrifugal force of 48,500 g for 2 hours; then decanting, andredispersion in DDI H₂O with ultrasonication before analysespreparations were performed. Centrifugations were performed in a BeckmanJ2-HS centrifuge at 20,500 rpm using a JA-21 rotor.

Using this method the final molar composition of a synthesis solutionbased on colloidal silica was in general about 1.00 Al₂O₃:50-200*(1-x)SiO₂(HS-30):50-200*(x) SiO₂(PETMS):18 (TEA)₂O (2OH⁻):0.55-2.22Na₂O:1000-1500 H₂O, x was varied between 0.005 and 0.25. And an examplesolution composition was 1.00 Al₂O₃:100*(1-x) SiO₂(HS-30):100*(x)SiO₂(PETMS):18 (TEA)₂O (2OH⁻):1.11 Na₂O:1330 H₂O, where x equals 0.005,with the weight composition as follows: (for x=0.005) 76.46 g TEAOH,12.5 g aluminum isopropoxide, 100.5 g Ludox HS-30, and 0.58 g phenethyltrimethoxysilane (PETMS).

Using this method the molar composition of a synthesis solution based onfumed silica was in general about 1.00 Al₂O₃:(v*(1-w)) SiO₂(fumedsilica):(v*w) SiO₂(PETMS):(0.26*v+1) (TEA)₂O (2OH⁻):(15*v) H₂O, wherethe total SiO₂/Al₂O₃ ratio is represented by the symbol v, and the molepercentage of total Si in the synthesis mixture provided by PETMS isrepresented by w. v was varied between 16 and 400 and w was variedbetween 0.01 and 0.20. An example solution with composition (for v=25,w=0.028) consisted of 20.15 g TEAOH, 0.1646 g aluminum powder, 4.96 gfumed SiO₂, and 0.54 g PETMS. Phenethyl functionization was verifiedusing Si magic angle spinning nuclear magnetic resonance imagingspectroscopy (Si²⁹ NMR). FIG. 4 shows a Si²⁹NMR analysis of thephenethyl functionalized zeolite BEA nanocrystals. The peak located at−65 ppm indicates the presence of zeolite framework Si atoms that arecovalently bonded to a phenethyl side chain. This verifies the properformation of the phenethyl functionalized zeolite BEA nanocrystals.Using peak area analysis it can also be concluded that approximately 6%of the Si atoms in the zeolite framework have phenethyl side chains.FIG. 5 is a transmission electron microscopy image of Phenethylfunctionalized zeolite BEA nanocrystals synthesized with the followingcomposition 1.00 Al₂O₃:(v*(1-w)) SiO₂(fumed silica):(v*w)SiO₂(PETMS):(0.26*v+1) (TEA)₂O (2OH⁻):(15*v) H₂O, where v=25, andw=0.028.

EXAMPLE Preparation of Acid Functionalized Colloidal ZeoliteNanocrystals

After synthesis of the phenethyl functionalized zeolite FAU(Y) and BEA,sulfonic acidification of the phenethyl groups was accomplished. Toaccomplish this effectively, the organic template (e.g., TMA and TEA)used during the nanocrystal syntheses had to be removed from the zeoliteframework. This had to be performed without damaging or agglomeratingthe crystals. Due to the high aluminum content of the zeolite FAU(Y)nanocrystals, mild pH ion exchangers like NaNO₃ or NH₄NO₃ were used. Thezeolite FAU(Y) ion exchanges were accomplished with 2 wt % zeolite solidloading in the ion exchange solution and either 1M NaNO₃ or NH₄NO₃ asthe ion exchanger at 90° C. with magnetic bar stirring in atemperature-controlled bath. Once the template was removed, sulfonicacid groups were added to the phenethyl side chains of thefunctionalized zeolite FAU(Y), while maintaining the dispersability ofthe nanocrystals. First, the zeolite FAU(Y) nanocrystals weredealuminated to increase their acid stability by exchanging framework Alwith Si using an ammonium hexafluorosilicate (AHFS) treatment in aammonium acetate buffered suspension The second step of this techniquerequires the dealuminated, functionalized zeolite to be dispersed in achlorinated solvent such as methylene chloride in an anhydrousatmosphere. Sulfonation of the phenethyl functionalized zeolite Ynanocrystals was then performed with trimethyl silyl chlorosulfonate[(CH₃)₃SiSO₃Cl] in the chlorinated solvent suspension, then thenanocrystals were treated with sodium methoxide to obtain their sodiumform, which was then dispersed in DMF and converted to acid form bytitration with hydrochloric acid.

The high silica zeolite BEA nanocrystal material was resistant to acidconditions, and could withstand 100° C. treatments with concentratedsulfuric acid in order to remove the organic template, while maintainingsignificant crystallinity. This allowed both the template removal andthe sulfonic acidification of the zeolite BEA nanocrystals to occurduring the same concentrated sulfuric acid treatment. After sulfonicacidification of the zeolite BEA nanocrystals, the amount of sulfonicacid groups attached to the zeolite was determined to be 1.0076*10⁻³ molSO₃H per gram of zeolite by using 0.050 M NaOH titration technique witha phenolthalein indicator. This translates to an equivalent weight of992 g zeolite per mol SO₃H. This compares favorably with the equivalentweight of the Nafion (equivalent weight=1100 g Nafion per mol SO₃H) usedto make some of the nanocomposite membranes.

EXAMPLE Preparation of Polymer/Zeolite Nanocomposite Membrane

Zeolite Nanocrystal Synthesis

Zeolite FAU(Y) nanocrystals were synthesized according the methodsdisclosed above. Plain and phenethyl linked sulfonic acidified zeoliteBEA nanocrystal were synthesized according to the methods disclosedabove. Once synthesized, the clean zeolite nanocrystals were centrifugedat 48,500 g for 2 hours, the water in which they previously weredispersed in was removed, and then the nanocrystals were redispersed inethanol.

Membrane Casting

Membranes were cast in custom-made glass vessels. These vessels werecomposed of an aluminum fixture designed to compress a glass cylinderonto a flat plate glass bottom with a Teflon tape seal. Initialmembranes that were cast in petri dishes and glass beakers had thicknessvariations because those vessels were not flat-bottomed. Accuracy of themembrane characterization depends upon uniform membrane thickness, socasters with flat bottoms were a necessity. In general, the followingmembrane casting technique was followed. The source of polymer was aNafion suspension from Dupont. Zeolite nanocrystals in ethanolsuspension were added to the Nafion suspension and the solventcomposition of the mixture was augmented to achieve ideal membranecasting conditions. Following are examples of successful recipes forcasting homogenous zeolite/polymer nanocomposite membranes.

Homogenous nanocomposite membranes with zeolite Y nanocrystals andNafion were cast in the H⁺ form using the following procedure. Plainzeolite Y nanocrystals were first ion exchanged using a 12 hour aqueous1M NaNO₃ treatment at 80° C. with stirring in order to remove thetemplate TMA⁺ from the supercages in micropore structure of the zeolitenanocrystals. After ion exchange, the zeolite Y nanocrystals werecentrifuged 3 times with relative centrifugal force of 48,500 g for 2hours. After the first two centrifugation, the zeolite Y nanocrystalswere redispersed in DDI H₂O. After the third centrifugation, the zeoliteY nanocrystals were dispersed in ethanol (200 proof). Centrifugationswere performed in a Beckman J2-HS centrifuge at 20,500 rpm using a JA-21rotor. The resulting zeolite Y suspension contained 1.15 wt % zeolite Ynanocrystals in ethanol. The original Nafion solution obtained from DuPont (referred to as “raw Nafion” from now on) was composed of 5 wt %Nafion polymer (1100 equivalent weight), <5% methanol, 30-60% water,15-30% 1-propanol, and 15-30% 2-propanol. The raw Nafion solution was inits acid counterbalanced (H⁺) form. The raw Nafion solvent compositionled to poor membrane casting, therefore a Nafion/ethanol suspension wasgenerated by first drying raw Nafion solution. The dry Nafion was thentreated with 25 wt % nitric acid (aqueous) at 80° C. for 2 hours,followed by repeated rinsing with DDI H₂O. The Nafion (H⁺-form) was thenput into ethanol (200 proof) and stirred in a temperature bath at 80° C.to redisperse the polymer. The resulting Nafion in ethanol suspensionconsisted of 7.8 wt % Nafion and 92.2 wt % ethanol. The final membranecasting composition to yield a 10 wt % zeolite Y in Nafion membrane withthickness of approximately 180 micrometers in a cylindrical glasscasting vessel of inner diameter 66 millimeters is as follows: 13.62 gof 7.8 wt % Nafion in ethanol, 10.26 g of 1.15 wt % zeolite Y inethanol. The final suspension contained 1.0620 g Nafion, 0.1180 gzeolite Y, and 22.6933 g ethanol. The casting vessel was then coveredwith a watch glass and then put on a level surface in a vacuumdesiccator operating at room temperature. The casting vessel was removedwhen the solvent was completely removed from the casting suspension.Solvent removal required 3-4 days. The casting vessel was then put in aconvection oven for one day at 140° C. for the final temperaturetreatment of the cast membrane.

Homogenous nanocomposite membranes with plain zeolite BEA nanocrystalsand Nafion were cast in the H⁺ form using the following procedure. Plainzeolite BEA nanocrystals were first ion exchanged using a 12 hour 96 wt% sulfuric acid treatment (2 wt % zeolite) at 80° C. with stirring inorder to remove the template TEA⁺ from the micropore structure of thezeolite nanocrystals. After ion exchange, the zeolite BEA nanocrystalswere centrifuged 3 times with relative centrifugal force of 48,500 g for2 hours. After the first two centrifugations, the zeolite BEAnanocrystals were redispersed in DDI H₂O. After the thirdcentrifugation, the zeolite BEA nanocrystals were dispersed in ethanol(200 proof). Centrifugations were performed in a Beckman J2-HScentrifuge at 20,500 rpm using a JA-21 rotor. The resulting zeolite BEAsuspension contained 0.57 wt % zeolite BEA nanocrystals in ethanol. Theoriginal Nafion solution obtained from Du Pont (referred to as “rawNafion”) was composed of 5 wt % Nafion polymer (1100 equivalent weight),<5% methanol, 30-60% water, 15-30% 1-propanol, and 15-30% 2-propanol.The raw Nafion solution was in its acid counterbalanced (H⁺) form. Theraw Nafion solvent composition led to poor membrane casting, therefore aNafion/ethanol suspension was generated by first drying raw Nafionsolution. The dry Nafion was then treated with 25 wt % nitric acid(aqueous) at 80° C. for 2 hours, followed by repeated rinsing with DDIH₂O. The Nafion (H⁺-form) was then put into ethanol (200 proof) andstirred in a temperature bath at 80° C. to redisperse the polymer. Theresulting Nafion in ethanol suspension consisted of 7.8 wt % Nafion and92.2 wt % ethanol. The final membrane casting composition to yield a 5wt % zeolite BEA in Nafion membrane with thickness of approximately 180micrometers in a cylindrical glass casting vessel of inner diameter 66millimeters is as follows: 14.37 g of 7.8 wt % Nafion in ethanol, 10.35g of 0.57 wt % zeolite BEA in ethanol, and 24.7227 g N,N-DMF. N,N-DMFacts as a high boiling aprotic cosolvent that helps cast homogenousmembranes using plain zeolite BEA. The final suspension contained 1.1210g Nafion, 0.05990 g zeolite BEA, 23.5427 g ethanol, and 24.7227 gN,N-DMF. The casting vessel was then covered with a watch glass and thenput on a level surface in a convection oven operating at 80° C. for 2days, followed by increasing the oven temperature to 100° C. for about 3days or until all solvent has be removed, and then finally increasingthe temperature to 140° C. for one day for the final temperaturetreatment of the cast membrane.

Homogenous nanocomposite membranes with acid functionalized zeolite BEAnanocrystals and Nafion were cast in the H⁺ form using the followingprocedure. Phenethyl functionalized zeolite BEA nanocrystals were firstion exchanged and acidified using a 12 hour 96 wt % sulfuric acidtreatment at 80° C. with stirring in order to remove the template TEA⁺from the micropore structure of the zeolite nanocrystals, while at thesame time adding SO₃H groups to the organic side chains located on thephenethyl functionalized zeolite BEA. After ion exchange, the acidifiedzeolite BEA nanocrystals were centrifuged 3 times with relativecentrifugal force of 48,500 g for 2 hours. After the first twocentrifugation, the acidified zeolite BEA nanocrystals were redispersedin DDI H₂O. After the third centrifugation, the acidified zeolite BEAnanocrystals were dispersed in ethanol (200 proof). Centrifugations wereperformed in a Beckman J2-HS centrifuge at 20,500 rpm using a JA-21rotor. The resulting acidified zeolite BEA suspension contained 0.68 wt% acidified zeolite BEA nanocrystals in ethanol. The original Nafionsolution obtained from Du Pont (referred to as “raw Nafion”) wascomposed of 5 wt % Nafion polymer (1100 equivalent weight), <5%methanol, 30-60% water, 15-30% 1-propanol, and 15-30% 2-propanol. Theraw Nafion solution was in its acid counterbalanced (H⁺) form. The rawNafion solvent composition led to good membrane casting with acidifiedzeolite BEA nanocrystals when N,N DMF was used as a cosolvent. N,N-DMFacts as a high boiling aprotic cosolvent that helps cast homogenousmembranes when using raw Nafion solutions. The final membrane castingcomposition to yield a 5 wt % acidified zeolite BEA in Nafion membranewith thickness of approximately 180 micrometers in a cylindrical glasscasting vessel of inner diameter 66 millimeters is as follows: 22.42 gof 5 wt % raw Nafion, 8.68 g of 0.68 wt % zeolite BEA in ethanol, and24.7227 g N,N-DMF. The final suspension contained 1.1210 g Nafion,0.0590 g acidified zeolite BEA, 8.6175 g ethanol, 21.2990 g raw Nafionsolvent mix, and 24.7227 g N,N-DMF. The casting vessel was then coveredwith a watch glass and then put on a level surface in a convection ovenoperating at 80° C. for 2 days, followed by increasing the oventemperature to 100° C. for about 3 days or until all solvent has beremoved, and then finally increasing the temperature to 140° C. for oneday for the final temperature treatment of the cast membrane.

Homogenous nanocomposite membranes with acid functionalized zeolite BEAnanocrystals and Nafion were cast in the H⁺ form using the followingprocedure. Phenethyl functionalized zeolite BEA nanocrystals were firstion exchanged and acidified using a 12 hour 96 wt % sulfuric acidtreatment at 80° C. with stirring in order to remove the template TEA⁺from the micropore structure of the zeolite nanocrystals, while at thesame time adding SO₃H groups to the organic side chains located on thephenethyl functionalized zeolite BEA. After ion exchange, the acidifiedzeolite BEA nanocrystals were centrifuged 3 times with relativecentrifugal force of 48,500 g for 2 hours. After the first twocentrifugation, the acidified zeolite BEA nanocrystals were redispersedin DDI H₂O. After the third centrifugation, the acidified zeolite BEAnanocrystals were dispersed in ethanol (200 proof). Centrifugations wereperformed in a Beckman J2-HS centrifuge at 20,500 rpm using a JA-21rotor. The resulting acidified zeolite BEA suspension contained 0.68 wt% acidified zeolite BEA nanocrystals in ethanol. The new Nafion solutionobtained from Du Pont (referred to as “Liquion”) was composed of 5 wt %Nafion polymer (1100 equivalent weight), 20% water, and 75% isopropanol.The Liquion Nafion solution was in its acid counterbalanced (H⁺) form.The Liquion solvent composition led to good membrane casting withacidified zeolite BEA nanocrystals. The final membrane castingcomposition to yield a 5 wt % acidified zeolite BEA in Nafion membranewith thickness of approximately 180 micrometers in a cylindrical glasscasting vessel of inner diameter 66 millimeters is as follows: 22.42 gof 5 wt % Liquion and 8.68 g of 0.68 wt % zeolite BEA in ethanol. Thefinal suspension contained 1.1210 g Nafion, 0.0590 g acidified zeoliteBEA, 8.6175 g ethanol, 4.4840 g water, and 16.8150 g isopropanol. Thecasting vessel was then covered with a watch glass and then put on alevel surface in a convection oven operating at 50° C. until all solventhas be removed, and then finally increasing the temperature to 140° C.for one day for the final temperature treatment of the cast membrane.

N,N DMF can also be used as a cosolvent when casting H⁺ form membranesusing acidified zeolite BEA in ethanol and Liquion suspensions, and ithas been shown to increase the amount of zeolite loading possible in acast homogenous membrane. For example, a homogenous membrane with 20 wt% zeolite in Nafion was cast using the following procedure. The finalmembrane casting composition to yield a 20 wt % acidified zeolite BEA inNafion membrane with thickness of approximately 180 micrometers in acylindrical glass casting vessel of inner diameter 66 millimeters is asfollows: 18.88 g of 5 wt % Liquion, 8.61 g of 2.74 wt % zeolite BEA inethanol, and 27.49 g N,N DMF. The final suspension contained 0.9940 gNafion, 0.2360 g acidified zeolite BEA, 8.3771 g ethanol, 3.7760 gwater, and 14.1600 g isopropanol. The casting vessel was then coveredwith a watch glass and put on a level surface in a convection ovenoperating at 80° C. for 2 days, followed by increasing the oventemperature to 100° C. for about 3 days or until all solvent has beremoved, and then finally increasing the temperature to 140° C. for oneday for the final temperature treatment of the cast membrane.

Homogenous nanocomposite membranes with acid functionalized zeolite BEAnanocrystals and Nafion were cast in the Na⁺ form using the followingprocedure. When higher membrane final treatment temperatures are neededthe Na⁺ form of the Nafion polymer is used for its higher thermalstability. Therefore, a direct membrane casting in the Na⁺ form isnecessary in some cases due to the fact that it is challenging to use amembrane treatment after casting to obtain its Na⁺ form without changingthe properties of the membrane. Phenethyl functionalized zeolite BEAnanocrystals were first ion exchanged and acidified using a 12 hour 96wt % sulfuric acid treatment at 80° C. with stirring in order to removethe template TEA⁺ from the micropore structure of the zeolitenanocrystals, while at the same time adding SO₃H groups to the organicside chains located on the phenethyl functionalized zeolite BEA. Afterion exchange, the acidified zeolite BEA nanocrystals were centrifuged 3times with relative centrifugal force of 48,500 g for 2 hours. After thefirst two centrifugation, the acidified zeolite BEA nanocrystals wereredispersed in DDI H₂O. After the third centrifugation, the acidifiedzeolite BEA nanocrystals were dispersed in ethanol (200 proof).Centrifugations were performed in a Beckman J2-HS centrifuge at 20,500rpm using a JA-21 rotor. The resulting acidified zeolite BEA suspensioncontained 0.68 wt % acidified zeolite BEA nanocrystals in ethanol. Thenew Nafion solution obtained from Du Pont (referred to as “Liquion”) wascomposed of 5 wt % Nafion polymer (1100 equivalent weight), 20% water,and 75% isopropanol. The Liquion Nafion solution was in its acidcounterbalanced (H⁺) form. The Liquion solvent composition led to goodmembrane casting with acidified zeolite BEA nanocrystals. After mixingof the Liquion, acidified zeolites, and N,N-DMF, and prior to pouring inthe casting vessel, the mixture was titrated to a pH of 7 with ethanolsolution saturated with NaOH. This ensured that the Nafion and acidifiedzeolite were counterbalanced by Na⁺ ions instead of H⁺. The finalmembrane casting composition to yield a 5 wt % acidified zeolite BEA inNafion membrane with thickness of approximately 180 micrometers in acylindrical glass casting vessel of inner diameter 66 millimeters is asfollows: 22.42 g of 5 wt % Liquion, 8.68 g of 0.68 wt % zeolite BEA inethanol, and 24.57 g N,N DMF. The final suspension contained 1.1210 gNafion, 0.0590 g acidified zeolite BEA, 8.6175 g ethanol, 4.4840 gwater, 16.8150 g isopropanol, and 24.5733 g N,N DMF. The casting vesselwas then covered with a watch glass and put on a level surface in aconvection oven operating at 80° C. for 2 days, followed by increasingthe oven temperature to 100° C. for about 3 days or until all solventhas be removed, and then finally increasing the temperature to 140° C.for one day for the final temperature treatment of the cast membrane.

After the membrane formation in the oven, the casting vessel was thenremoved from the oven and allowed to cool (if it was heated to obtainthe membrane). Once cool, DDI H₂O was poured in the vessel to loosen themembrane from the glass. To prepare the membrane for characterization,it was first boiled in 3 wt % H₂O₂ for one hour then rinsed with boilingDDI H₂O. Then it was boiled in a 0.5M sulfuric acid solution for onehour, followed by rinsing with boiling DDI H₂O. Finally, the membranewas boiled for 1 hour in DDI H₂O, then allowed to cool, after which themembrane was ready for testing.

The proton conductivity of the membrane was determined using 4-electrodeAC impedance spectroscopy similar to the technique in (Sone, Y., P.Ekdunge, and D. Simonsson, Proton conductivity of Nafion 117 as measuredby a four-electrode AC impedance method. Journal of the ElectrochemicalSociety, 1996, 143(4):1254-1259.)

The best performance was for a 5 wt % sulfonic acid functionalizedzeolite BEA membrane out of all those that were tested at both 21° C.and 77° C. The 5 wt % acid zeolite BEA/polymer nanocomposite membranepossessed a proton conductivity 27% higher than commercial Nafion 117 at21° C., and 18% higher than commercial Nafion 117 at 77° C.

Methanol crossover was determined using a 2-compartment diffusion cell,similar to the technique in Tricoli, V., Proton and methanol transportin poly(perfluorosulfonate) membranes containing Cs+ and H+ cations.Journal of the Electrochemical Society, 1998, 145(11):3798-3801. And the5 wt % sulfonic functionalized zeolite BEA was the best performingmembrane out of all those that were tested at both 21° C. and 77° C. The5 wt % acid zeolite BEA/polymer nanocomposite membrane possessed amethanol crossover 27% lower than commercial Nafion 117 at 21° C., and46% lower than commercial Nafion 117 at 77° C.

Likewise, the best proton conductivity/methanol permeability ratioobtained for the 5 wt % sulfonic acid zeolite BEA/Nafion nanocompositemembrane possessed a proton conductivity/methanol permeability ratio 70%high than commercial Nafion 117 at 21° C., and 110% higher thancommercial Nafion 117 at 77° C.

EXAMPLE Preparation of a Proton Exchange Membrane Fuel Cell Using theMembranes

The membrane electrode assemblies were prepared by sandwiching themembrane between two electrodes, and hot-pressing at 135° C./90 atm for90 s. The anode and cathode were prepared according to the proceduresreported by Wilson (U.S. Pat. No. 5,211,984 (1993)). The catalystloadings of anode (40% PtRu/C) and cathode (20% Pt/C) are 1 mg/cm² and0.4 mg/cm², respectively.

In-situ methanol crossover, proton conductivity (membrane resistance)and polarization curve were electrochemically investigated for plainNafion and zeolite modified membranes.

Crossover Measurement

Limiting current density of the methanol crossover through the membranewas measured by using the Solartron Electrochemical interface (SI1287)and PCT-2000 fuel cell test station (ElectroChem, USA). The 2M methanolsolution was fed to the anodic side of the MEA with 0 psig back pressurewhile the cathodic side was kept in an inert humidified N₂. By applyinga dynamic potential at the cathodic side, the methanol permeation fluxthrough the membrane can be expressed by the measuredtransport-controlled limiting current density of the methanolelectro-oxidation process at the Pt/membrane interface of the cathodicside. The true crossover current at open circuit is further obtainedafter the correction of back electro-osmotic drag. The anode, wherehydrogen evolution took place, served as the counter electrode as wellas dynamic hydrogen reference electrode (DHE). The experiments wereconducted at different temperatures and concentrations to determinetheir influence on the limiting current density.

Impedance and Polarization Measurement

The same PCT-2000 fuel cell test station was used for the cellpolarization testing, except that humidified oxygen was preheated to thecell temperature and fed to the cathode at 200 ml/min with 26 psig backpressure. In-situ membrane resistances were measured by impedancespectroscopy using the Solartron Electrochemical interface (SI1287),Solartron impedance analyzer (SI1260) at a frequency range of 1 Hz˜10kHz.

Results

The tables below summarize the results for the methanol crossover andproton conductivity measurements for DMFCs.

Methanol Crossover Measurement for Direct Methanol Fuel Cell (DMFC)

Methanol crossover measurement for direct methanol fuel cell (DMFC)Crossover current (A) 70° C. 50° C. 30° C. 25° C. Nafion 117 (N117-1)0.91 0.59 0.32 0.28 modified 2.5% (M2.5-1) 0.31 0.28 0.15 0.13 modified5% (M5-1) 0.37 0.34 0.21 0.19 Improvement (%), M2.5-1 66 53 52 53Improvement (%), M5-1 60 44 44 43

Both the 2.5% and 5% modified membrane show 40-60% improvement in termsof the blocking of methanol crossover.

Proton conductivity measurement for DMFC 70° C. 50° C. 30° C. 25° C.Resistance (Ohm) N117 0.234 0.251 0.257 0.264 M2.5-1 0.227 0.228 0.2490.254 M5-1 0.246 — — 0.267 Conductivity (S/cm) N117 0.033 0.029 0.0270.025 M2.5-1 0.039 0.039 0.031 0.030 Improvement (%), M2.5-1 17.8 33.817.1 18.4 Improvement (%), 5% No No

The 2.5% modified membrane shows significant improvements in performanceover that of the plain commercial Nafion 117. However, the 5% modifiedmembrane shows no improvement in the proton conductivity.

Polarization Curve Measurement for DMFC

Significant cell performance improvement is observed for acidfunctionalized zeolite modified membrane as shown in FIG. 1. FIG. 1 is apolarization curve for DMFCs with different membranes, obtained for thefollowing operating conditions: 70° C., oxygen pressure 26 psi; anode: 1mg/cm² 40% PtRu/C; cathode: 0.5 mg/cm², 20% Pt/C.

The enhanced proton conductivity and lowered methanol crossover comparedwith Nafion are observed for the zeolite-modified membrane. To explainthese, a better understanding about the structure of Nafion is required.

Nafion membrane consists of hydrophobic PTFE backbone and hydrophilicpendant side chains terminated by sulfonate ionic groups. Comprising upto 15% of the polymer, the —SO₃H groups would dissociate in polarsolvent and protonate the solvent. Experimental results suggest that thenegatively charged —SO₃ ⁻ groups, along with water molecules andprotons, tend to aggregate and form hydrophilic clusters, which areeither dispersed in the continuous hydrophobic PTFE matrix or form acontinuous phase and interpenetrate with the PTFE matrix, depending onthe hydration level. The protonated solvent species within the connectedclusters or channels serves as the major charge carrier in the membranevia hopping mechanism or vehicle mechanism. Water or methanol transportthrough the membrane is accomplished by moving through the ion-clusterpores and the connecting ion channels, or in more general way, throughthe hydrophilic network, while in the hydrophobic PTFE region bothmethanol and water have negligible solubility.

When zeolite particles are incorporated in the membrane, due to thehydrophilic property, they have a tendency to stay in the hydrophilicregion of the membrane, which would affect the structure of the Nafion.Nafion is a random copolymer of perfluoroethylene units and ionomericunits. It has been shown that in a Nafion membrane a significant portion(approximately 20%) of the sulfonic acid groups are buried within theclusters of hydrophobic regions of the perfluoroethylene backbone, andare unused for proton transport. One possible reason for the enhancedproton conduction is that the introduction of the acid functionalizedzeolite nanocrystals causes an increase in ordering during the castingprocess or allows more ionic groups located within the vicinity of thehydrophilic particle surface to be exposed, instead of being buriedunderneath the PTFE backbone, which results in the acid groups of theNafion polymer being more accessible for proton transport.

The lowered methanol crossover can be explained by the blocking of thehydrophilic channel with the zeolite particles. It should be mentionedthat the sulfonic acid functionalized zeolite has a porous structure.Although the pore size is not small enough to physically exclude thetransport of methanol or water, it is believed the transport rate ofthese small molecules through the porous structure is drasticallyreduced. The reason is that the motion of the water initially existingin the pores is restricted and the water is actually trapped inside thepores which blocks the transport of small molecules. However, the protonconduction is not impeded by the existence of zeolite particles. Undersuch circumstance, it is believed that hopping mechanism is thepredominant working mechanism, where the proton conduction is realizedby the proton jumping from hydronium ion to the proton accepting watermolecule adjacent to the sulfonic groups without the bodily drift of thehydronium (therefore no net water movement through the pores). Thevehicular mechanism that requires the existence of mobile bulk-likewater molecules to travel along with protons is unfavored because of thelack of mobile water molecules. The bounded movement of the methanolwith proton due to the electro-osmotic drag is also mitigated with theintroduction of zeolite.

The above bases can be used for the explanation of the slightimprovement of proton conductivity when the membranes are subject toinsufficient hydration at high temperature. At such condition, it isknown that the membrane is in lack of mobile bulk-like water molecules.

The introduction of sulfonic acid functionalized zeolite may allow theproton transport surrounding the zeolite to proceed more preferentiallyvia the hopping mechanism than the vehicular mechanism as it adsorbswater or place restriction on the motion of water molecules. The overalleffect is the mitigated dragging of the water by the proton andtherefore the improved proton conductivity.

The performance of the fuel cell using the membrane in accordance withthe embodiments of the present invention constructed with a 5 wt % acidzeolite BEA/polymer nanocomposite membrane was enhanced over that of aMEA using a Nafion 117 membrane, as indicated by a 10% higher poweroutput at 60 mA/cm² and a 32% higher power output at 120 mA/cm². With a2.5 wt % acid zeolite BEA/polymer nanocomposite membrane, 37% higherpower output at 60 mA/cm² and a 90% higher power output at 120 mA/cm²was observed. This operation data was obtained at 70° C. and 26 psipressurization; the anode of 40% PtRu/C, 1.0 mg/cm² and a cathode ofcathode: 20% Pt/C, 0.4 mg/cm². Varying the operation temperature of theDMFC, methanol crossover current in A/cm² was determined usingpotentiodynamic sweeping to be approximately 40% that of a MEA made withNafion 117 as the proton conducting membrane.

As will be understood by those skilled in the art, the present inventionmay be embodied in other specific forms without departing from theessential characteristics thereof. For example, steps may be combined orexpanded during the synthesis of the nanocomposite membranes. Theseother embodiments are intended to be included within the scope of thepresent invention, which is set forth in the following claims.

1. A method of forming a polymer/zeolite nanocomposite membrane,comprising: forming a zeolite nanocrystal suspension; forming a polymersource suspension; combining the zeolite nanocrystal suspension with thepolymer source suspension; ultrasonicating the resulting solution;pouring the resulting solution into a casting vessel; heating the pouredsolution in the casting vessel until the solution is dry; heat treatingthe dried solution; cooling the casting vessel; and removing the formedpolymer/zeolite nanocomposite membrane.
 2. The method of claim 1 whereinthe size of the zeolite nanocrystal particles are comparable with domainsize of the host polymer.
 3. The method of claim 1 wherein the polymeris a film forming fluorinated sulfonic acid containing copolymer.
 4. Themethod of claim 1 wherein the polymer is selected from the groupconsisting of a Teflon type polymer, perfluorinated polymer, andperfluorinated polymer with sulfonic groups.
 5. The method of claim 1wherein the weight ratio of the zeolite nanocrystals to that of thepolymer in the polymer/zeolite nanocomposite membrane is between aweight ratio of 98.75 wt % polymer and 1.25 wt % zeolite nanocrystal to60 wt % polymer and 40 wt % zeolite nanocrystal.
 6. The method of claim1 wherein the formed polymer/zeolite nanocomposite membrane is a protonconductor.
 7. The method of claim 2 wherein the membrane has a protonconductivity of between 2 and 7×10⁻² S/cm.
 8. The method of claim 2wherein the membrane has methanol permeability of less than between 0.8to 5.7×10⁻⁶ cm²/s.
 9. The method of claim 2 wherein the membrane has aproton conductivity to permeability ratio of more than between 0.8 to5.8×10⁴ S sec/cm³.
 10. The method of claim 1 wherein said forming azeolite nanocrystal suspension comprises adding the zeolite nanocrystalsto a substance selected from the group consisting of ethanol, methanol,isopropanol, N,N dimethylformamide and water.
 11. The method of claim 1wherein the polymer source solution solvent mixture consists of one orseveral of the following: methanol, ethanol, isopropanol, N,Ndimethylformamide and water.
 12. The method of claim 1 wherein saidforming comprises forming phenethyl functionalized zeolite FAU(Y)nanocrystals.
 13. The method of claim 12 wherein said forming phenethylfunctionalized zeolite FAU(Y) nanocrystals comprises: combining asolution comprising of double de-ionized water, 25 wt % aqueoustetramethylammonium hydroxide solution and an appropriate amount ofaluminum isopropoxide; stirring the solution until it is opticallyclear; adding and dissolving an amount of tetramethylammonium bromide inthe solution; adding an amount of aqueous colloidal silica to thesolution; adding an appropriate amount of phenethyl trimethoxysilane toform a completed solution; sealing the completed solution; aging andstirring the completed solution; and heating and stirring the completedsolution to form the phenethyl functionalized zeolite FAU(Y)nanocrystals.
 14. The method of claim 13 further comprising formingsulfonic acid functionalized zeolite FAU(Y) nanocrystals using thephenethyl functionalized zeolite FAU(Y) nanocrystals, by: removing thetetramethylammonium organic template of the nanocrystals by an ionexchange process to form ion exchanged nanocrystals; and adding sulfonicacid groups to the ion exchanged nanocrystals by an acidificationtechnique to form the sulfonic acid functionalized zeolite FAU(Y)nanocrystals.
 15. The method of claim 1 wherein said forming comprisesforming phenethyl functionalized zeolite BEA nanocrystals.
 16. Themethod of claim 15 wherein said forming phenethyl functionalized zeoliteBEA nanocrystals, comprises: combining a solution comprising of doublede-ionized water, 35 wt % aqueous tetraethylammonium hydroxide solution,and an appropriate amount of aluminum isopropoxide; stirring thesolution until it is optically clear; adding an appropriate amount ofaqueous 30 wt % colloidal silica; adding an appropriate amount ofphenethyl trimethoxysilane to form a completed solution; sealing thecompleted solution; aging and stirring the completed solution; andheating and stirring the completed solution to from the phenethylfunctionalized zeolite BEA nanocrystals.
 17. The method of claim 15wherein said forming phenethyl functionalized zeolite BEA nanocrystals,comprises: forming an aluminum precursor solution; forming a silicaprecursor solution; stirring the aluminum precursor solution until it isoptically clear; combining the aluminum precursor and the silicaprecursor solutions to form a combined solution; mixing the combinedsolution together; sealing the combined solution to form a sealedcombined solution; and reacting the sealed combined solution to form thephenethyl functionalized zeolite BEA nanocrystals.
 18. The method inaccordance with claim 16 further comprising forming sulfonic acidfunctionalized zeolite BEA nanocrystals using the phenethylfunctionalized zeolite BEA nanocrystals, by: acid treating saidphenethyl functionalized zeolite BEA nanocrystals in a concentratedsulfuric acid environment, thus both removing the tetramethylammoniumorganic template of the nanocrystals, and adding sulfonic acid groups tothe nanocrystals to form the sulfonic acid functionalized zeolite BEAnanocrystals.
 19. The method of claim 1 wherein said forming a polymersource suspension comprises adding the polymer source to a substanceselected from the group consisting of ethanol, methanol, isopropanol,N,N dimethylformamide and water.
 20. The method of claim 1 wherein saidheating comprises heating the poured solution in the casting vessel on alevel surface at a temperature of about 80° C. for a time period ofbetween one hour to 5 days so as to form a gel.
 21. The method of claim20 further comprising heating the poured solution in the casting vesselat a temperature of about 100° C. for a time period of between one hourto 5 days so as to boil off the high boiling point solvent.
 22. Themethod of claim 1 wherein said heat treating comprises heating thepoured solution in the casting vessel at a temperature of about 140° C.for a time period of between one hour to 5 days.
 23. The method inaccordance with claim 17 further comprising forming sulfonic acidfunctionalized zeolite BEA nanocrystals using the phenethylfunctionalized zeolite BEA nanocrystals, by: acid treating saidphenethyl functionalized zeolite BEA nanocrystals in a concentratedsulfuric acid environment, thus both removing the tetramethylammoniumorganic template of the nanocrystals, and adding sulfonic acid groups tothe nanocrystals to form the sulfonic acid functionalized zeolite BEAnanocrystals.